WO2021046548A1 - Revêtements barrières thermiques pour moteurs à combustion interne - Google Patents

Revêtements barrières thermiques pour moteurs à combustion interne Download PDF

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Publication number
WO2021046548A1
WO2021046548A1 PCT/US2020/049771 US2020049771W WO2021046548A1 WO 2021046548 A1 WO2021046548 A1 WO 2021046548A1 US 2020049771 W US2020049771 W US 2020049771W WO 2021046548 A1 WO2021046548 A1 WO 2021046548A1
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Prior art keywords
thermal
coating
barrier coating
thermal barrier
insulating
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PCT/US2020/049771
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English (en)
Inventor
Eric Jordan
Chen Jian
Rishi Kumar
Balakrishnan Nair
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The University Of Connecticut
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Priority to EP20861415.6A priority Critical patent/EP4017923A4/fr
Publication of WO2021046548A1 publication Critical patent/WO2021046548A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B77/00—Component parts, details or accessories, not otherwise provided for
    • F02B77/11—Thermal or acoustic insulation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • F01L3/04—Coated valve members or valve-seats
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • F02F3/12—Pistons  having surface coverings on piston heads
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2820/00—Details on specific features characterising valve gear arrangements
    • F01L2820/01—Absolute values
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • F02F3/12—Pistons  having surface coverings on piston heads
    • F02F3/14—Pistons  having surface coverings on piston heads within combustion chambers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2203/00—Non-metallic inorganic materials
    • F05C2203/08—Ceramics; Oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2251/00—Material properties
    • F05C2251/04—Thermal properties
    • F05C2251/042—Expansivity
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2251/00—Material properties
    • F05C2251/04—Thermal properties
    • F05C2251/048—Heat transfer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2253/00—Other material characteristics; Treatment of material
    • F05C2253/12—Coating

Definitions

  • IC engines dominate the ground transportation sector in the US (and globally), annually transporting 11 billion tons of freight and logging 3 trillion vehicle miles. Improvement to the fuel efficiency of IC engines reduces environmental impact and can yield large economic benefits, both to the end users (i.e., the operators of IC engine powered vehicles) and to the competitiveness of engine manufacturers across the world. Although U.S. federal regulations currently incentivize electric vehicles and the penetration of electric vehicles is expected to increase in the future, IC engines are anticipated to remain as the primary energy conversion technology in vehicle application to 2040 and beyond in nearly all projections.
  • TBCs Thermal barrier coatings
  • low thermal inertia TBCs provide rapid surface temperature response which will reduce time to catalyst light-off, resulting in lower unbumed hydrocarbon (UBHC) and carbon monoxide (CO) emissions during a cold-start.
  • UBHC unbumed hydrocarbon
  • CO carbon monoxide
  • the thermal barrier coating includes an insulating thermal spray coating, where a chosen material of the insulating thermal spray coating has a thermal conductivity lower than 2 W/mK in fully dense form and the chosen material includes a coefficient of thermal expansion within 5 ppm/K of a coefficient of thermal expansion of a material of a component of the internal combustion engine upon which the coating is placed.
  • the insulating thermal spray coating comprises a perovskite material.
  • the perovskite material is of the A 2 B 2 O 9 category, where A and B are cations.
  • the preceding subject matter of this paragraph characterizes example 3 of the present disclosure, wherein example 3 also includes the subject matter according to any one of examples 1-2, above.
  • the insulating thermal spray coating comprises lanthanum molybdate (La 2 Mo 2 O 9 .
  • the insulating thermal spray coating comprises lanthanum molybdate (La 2 Mo 2 09) with at least one dopant, wherein the dopant is one of Bi, Ni, Rb, Y, Gd, Nd, Ba, Sr, Ca.
  • the dopant is one of Bi, Ni, Rb, Y, Gd, Nd, Ba, Sr, Ca.
  • the insulating thermal spray coating comprises gadolinium zirconate (Gd 2 Zr 2 0 7 ).
  • the insulating thermal spray coating comprises lanthanum strontium cobalt ferrites, of the type La y Sri y Co 1-x Fe x O 3 oxides.
  • example 8 of the present disclosure, wherein example 8 also includes the subject matter according to any one of examples 1-7, above.
  • the insulating thermal spray coating comprises a material from the sodium zirconium phosphate (“NZP”) class of ceramics that have a single crystal coefficient of thermal expansion below 5 ppm/K.
  • NZP sodium zirconium phosphate
  • the material from the sodium zirconium phosphate (“NZP”) class of ceramics is one of Sro.5Hf 2 (P0 4 ) 3 , Sro.5Zr 2 (PO 4 ) 3 , Cao.25Sro. 25 Zr 2 (P0 4 ) 3 , CsHf 2 (P0 4 ) 3 , Ca 0.25 Sr 0.25 Zr 2 (P0 4 ) 3 , Cs 1.3 Gd 0.3 Zr 1.7 (P0 4 ) 3 .
  • the preceding subject matter of this paragraph characterizes example 10 of the present disclosure, wherein example 10 also includes the subject matter according to any one of examples 1-9, above.
  • the insulating thermal spray coating comprises calcium hexa- aluminate.
  • the component is steel and the insulating thermal spray coating comprises a material from the sodium zirconium phosphate (“NZP”) class of ceramics that have relatively low single crystal coefficient of expansion below 5 ppm/K.
  • NZP sodium zirconium phosphate
  • the material from the sodium zirconium phosphate (“NZP”) class of ceramics is one of Sr 0.5 Hf 2 (PO 4 ) 3 , Sr 0.5 Zr 2 (PO 4 ) 3 , Ca 0.25 Sr 0.25 Zr 2 (PO 4 ) 3 , CsHf 2 (PO 4 ) 3 , Cao.25Sro.25Zr2(P0 4 ) 3 , Csi. 3 Gdo. 3 Zri.7(P0 4 ) 3 .
  • the preceding subject matter of this paragraph characterizes example 13 of the present disclosure, wherein example 13 also includes the subject matter according to any one of examples 1-12, above.
  • the thermal barrier coating includes surface treatments through application of a top layer to enhance smoothness or enhance erosion resistance or reduce surface porosity.
  • the thermal barrier coating includes a material to absorb thermal radiation at or near a surface of the insulating thermal spray coating.
  • the material to absorb thermal radiation is one of Phosphor bonded AI 2 O 3 , Phosphor bonded Cr or Fe doped AI2O3, Phosphor bonded SiO 2 , Phosphor bonded Cr or Fe doped S1O2, Phosphor bonded ZrO 2 , Phosphor bonded Cr or Fe doped ZrO 2 , or calcium magnesium aluminosilicate glass.
  • the material further comprises silicon carbide or silicon nitride.
  • the component is one of a piston crown, a combustion chamber, a valve face, an exhaust port, or an exhaust manifold section.
  • the preceding subject matter of this paragraph characterizes example 18 of the present disclosure, wherein example 18 also includes the subject matter according to any one of examples 1-17, above.
  • a method for forming a thermal barrier coating is disclosed. The method includes applying an insulating thermal spray coating where a chosen material of the insulating thermal spray coating has a thermal conductivity lower than 2 W/mK in fully dense form and the chosen material includes a coefficient of thermal expansion within 5 ppm/K of a coefficient of thermal expansion of a material of a component of the internal combustion engine upon which the coating is placed.
  • the preceding subject matter of this paragraph characterizes example 19 of the present disclosure.
  • the method includes polishing the insulating thermal spray coating.
  • Figure 1 depicts a schematic diagram illustrating an embodiment of a thermal barrier coating in accordance with one or more embodiments of the present invention
  • Figure 2 depicts a schematic diagram illustrating an embodiment of a thermal barrier coating in accordance with one or more embodiments of the present invention
  • Figure 3 depicts a schematic diagram illustrating an embodiment of a substrate with an insulating thermal spray coating in accordance with one or more embodiments of the present inventions.
  • Figure 4 depicts a flow chart diagram of a method for forming a thermal barrier coating in accordance with one or more embodiments of the present invention.
  • an arrow may indicate a waiting or monitoring period of unspecified duration between enumerated steps of the depicted method.
  • the order in which a particular method occurs may or may not strictly adhere to the order of the corresponding steps shown.
  • TBCs can be used to address this issue.
  • heat losses can be substantially reduced, thereby providing higher temperatures and pressures after combustion and throughout expansion.
  • the higher pressures during expansion increase work extraction improving thermal efficiency.
  • low thermal inertia TBCs provide rapid surface temperature response which will reduce time to catalyst light-off, resulting in lower unburned hydrocarbon (UBHC) and carbon monoxide (CO) emissions during a cold-start.
  • UHC unburned hydrocarbon
  • CO carbon monoxide
  • TBCs in IC engines have been tested in the past, as early as the 1980s, in diesel engines, with the goal of duplicating the successful use of TBCs in gas turbines. This resulted in the concept of the adiabatic engine, where the basic premise was that insulating the combustion chamber would reduce heat rejection and consequently increase work generated by the cycle. Very thick ceramic coatings (in most cases, yttria- stabilized zirconia, YSZ) were applied to the cylinder head, and the top of the piston. However, this approach was largely unsuccessful due to four fundamental flaws:
  • Embodiments of the invention described herein differ significantly by elevating wall temperatures only when it matters most, i.e. during combustion and expansion, thus avoiding these negative effects.
  • a low thermal inertia coating can reduce emissions during cold-starts.
  • a large fraction of the UBHC and CO emissions during a standard EPA test can be attributed to the first 60 seconds of operation. After that initial period, the catalytic converter achieves the light-off temperature and begins reacting and reducing all but trace amounts of emissions.
  • TBCs have much lower thermal inertia than steel or aluminum, thus producing high surface temperatures soon after a cold-start along with reducing heat transfer losses, both of which will reduce the time to catalyst light-off and the cold-start emissions.
  • Embodiments described herein improve cold-starts and improve catalytic effects of TBCs, especially on the exhaust valves, which is particularly useful in cold-starts.
  • thermal inertia (also referred to as effusivity, which appears in the analytical solution to transient heat transfer problems with a periodic heat flux) is defined as the square root of the product of thermal conductivity and volumetric heat capacity.
  • Bi-LMO bismuth-doped La2Mo209
  • a coating effusivity of 620 J/m 2 -K-s 1 ⁇ 2 which is more than 40% lower than LSCF, 3X times lower than YSZ, and 2X lower than the highest performing coatings of GZO ( effusivity of 1364 J/m 2 - K-s 1 ⁇ 2 ).
  • Bi-LMO was down- selected due to its good durability in engine tests including associated water vapor and oil contaminants and its exceptionally low thermal inertia. This material is also stable up to at least 1000°C, and therefore, higher temperatures due to larger temperature swing in an SI engine will not be an issue.
  • only piston crowns are coated.
  • other components including the cylinder head, valve faces, and the fillet and lower stem of the intake and exhaust valves are coated. Coating additional components is guaranteed to further reduce heat loss and increase efficiency.
  • the firedeck is coated which can provide additional improvements.
  • Embodiments of this invention relate to thermal barrier coatings in internal combustion engines.
  • FIG. 1 a schematic diagram 100 of a spray coating is depicted.
  • the spray coating is applied through an air plasma spray (APS) process involving the injection of powder in a plasma plume.
  • APS air plasma spray
  • the schematic diagram includes a plasma gun 120 configured to spray a plasma.
  • a powder feeder 110 and feed port 115 that is configured to feed a powder 140 precursor into the plasma spray which sprays particles 143 (sometimes molten particles) onto the substrate 180 which forms an insulating thermal spray coating 170 on the substrate.
  • the substrate 180 may be any component part of an internal combustion engine including but not limited to a piston crown, a combustion chamber, a valve face, an exhaust port, an exhaust manifold section, a firedeck, etc.
  • the insulating thermal spray coating 170 may be applied to a single component or surface of an internal combustion engine or up to an entirety of an internal combustion engine.
  • a schematic diagram 200 of a spray coating is depicted.
  • the spray coating is applied through a solution precursor plasma process (SPPS).
  • SPPS solution precursor plasma process
  • the schematic diagram includes a plasma gun 120 configured to spray a plasma.
  • liquid reservoirs 111a and 111b which are fed via feed port 115 and injector 117 into the plasma spray.
  • the droplets 143 are applied to the substrate 180 to form an insulating thermal spray coating 170 or just coating.
  • arrows that represent a temperature control that may be applied to the substrate 180.
  • the system may also include a monitoring device 190 that is configured to monitor the injection process.
  • the SPPS process injects a solution precursor into the plasma plume in place of powder used in the APS process.
  • the SPPS process is used to rapidly spray and test new coating compositions, which allows the quick and efficient spray application of new compositions.
  • the alternative APS process requires powders of specific size distributions to be made which takes 2 to 3 months to make per batch. This is a time consuming and expensive process when compositions have to be modified during exploratory development work.
  • a second aspect of the coating properties that affects performance is surface roughness which showed that smoother surfaces improved performance. Roughness was routinely measured and is a candidate for optimization because spray parameters will influence roughness. Specifically, using smaller powder particles and as normal spray arrival angle as possible minimize surface roughness. In addition to directly helping cold start emissions, our low thermal inertia coatings reduce time to catalyst light-off and reduce cold-start emissions. Additionally, in some embodiments, thin surface catalyst coatings reduce cold-start emissions.
  • Economics of the deposition process will be enhanced by achieving repeatability of microstructure and consistency of microstructure over the complex part geometries. The process is reliable enough to minimize inspection requirements. Economics are also strongly affected by deposition rate and deposition efficiency.
  • Some embodiments include optimizing the characteristics needed for a particular performance of an engine. Variations of materials described herein provide different benefits. Options can be down-selected depending on the weighing factors that are most meaningful to the application.
  • the coating technology developed described here are a key technology for the improved performance of IC engines in terms of increased overall engine efficiency and reduced exhaust emissions. Considering that IC engines dominate the US ground transportation market and are expected to continue to do so for the foreseeable future, this technology will bring significant environmental and economic benefits, such as:
  • Some embodiments include significant thermal efficiency improvements that have been demonstrated for a compression ignition gasoline engine (homogeneous charge compression ignition (HCCI)) by the application of a thermal barrier coating (TBC) on the piston crown. This is accomplished by a temperature swing that reduces heat loss during the ignition part of the cycle but cools fast enough to avoid significant intake charge preheating.
  • the desired properties of the coating are low thermal energy storage and, hence, low mass density and specific heat, low thermal conductivity and sufficient strength to withstand the pressure excursion and thermal shock.
  • coating surface smoothness is important. The ideas presented herein are applicable to all gasoline compression ignition engines including but not limited to HCCI engines, diesel engines, and conventional spark ignition engines.
  • Embodiments of inventions described herein relate to a series of novel materials choices and material application methods to produce superior IC engine coatings.
  • these coatings may be applied by the thermal spray process.
  • the thermal spray process includes plasma spray, high velocity oxygen fuel spray, flame spray, detonation gun spray and vacuum and inert environment plasma spray. Because the metal in IC engines are aggressively cooled, the difference in thermal expansion coefficient between the coating and the metal, although still important, is less important than in gas turbines.
  • Thermal spray can be done by the following spray technologies, Plasma spray, high velocity oxygen fuel spray (HVOF), subsonic oxygen fuel spray, air fuel spray often called flame spray and detonation gun spray.
  • thermal spray is to be defined to specifically include any or all of these technologies.
  • the materials can be delivered to the thermal spray torch in three different forms, as a powder (PS), as a suspension of the material (SP), and as chemical precursors that form the final materials in reactions occurring in the thermal spray plume (PR).
  • PR specifically includes but is not limited to solution precursor plasma spray (SPPS)
  • SPPS solution precursor plasma spray
  • FIG. 3 a schematic diagram illustrating an embodiment of a substrate 180 with an insulating thermal spray coating 170 is depicted.
  • the substrate 180 is a component or portion of an internal combustion engine.
  • the thermal barrier coating includes an insulating thermal spray coating 170, where a chosen material of the insulating thermal spray coating 170 has a thermal conductivity lower than 2 W/mK in fully dense form and the chosen material includes a coefficient of thermal expansion within 5 ppm/K of a coefficient of thermal expansion of a material of a component of the internal combustion engine upon which the coating is placed.
  • Various ranges are contemplated including a thermal conductivity lower than 1 W/mK, 2 W/mK, 3 W/mK, 5 W/mK, 10 W/mK, 20 W/mK, or 50 W/mK.
  • Various ranges of CTE are contemplated including within 2 ppm/K, 5 ppm/K, 10 ppm/K, 20 ppm/K, or 50 ppm/K.
  • the insulating thermal spray coating 170 comprises a perovskite material.
  • the perovskite material is of the A2B2O9 category, where A and B are cations.
  • the insulating thermal spray coating 170 comprises lanthanum molybdate (La 2 Mo 2 O 9 ). In some embodiments, the insulating thermal spray coating 170 comprises lanthanum molybdate (La 2 Mo 2 O 9 ) with at least one dopant, wherein the dopant is one of Bi, Ni, Rb, Y, Gd, Nd, Ba, Sr, Ca.
  • the insulating thermal spray coating 170 comprises a material from the sodium zirconium phosphate (“NZP”) class of ceramics that have a single crystal coefficient of thermal expansion below 5 ppm/K.
  • NZP sodium zirconium phosphate
  • the material from the sodium zirconium phosphate (“NZP”) class of ceramics is one of Sr 0.5 Hf 2 (PO 4 ) , Sr 0.5 Zr 2 (PO 4 ), Ca 0.25 Sr 0.5 Zr 2 (PO 4 ), CsHf 2 (PO 4 ) 3 , Ca 0.25 Sr 0.5 Zr 2 (PO 4 ), Cs 1.3 Gd 0.3 Zr 1.7 (PO 4 ) 3 .
  • the insulating thermal spray coating 170 comprises calcium hexa-aluminate.
  • the component or substrate 180 is steel and the insulating thermal spray coating 170 comprises a material from the sodium zirconium phosphate (“NZP”) class of ceramics that have relatively low single crystal coefficient of expansion below 5 ppm/K.
  • NZP sodium zirconium phosphate
  • the material from the sodium zirconium phosphate (“NZP”) class of ceramics is one of Sr 0.5 Hf 2 (PO 4 ) , Sr 0.5 Zr 2 (PO 4 ), Ca 0.25 Sr 0.5 Zr 2 (PO 4 ), CsHf 2 (P0 4 ) 3 , Ca 0.25 Sr 0.5 Zr 2 (PO 4 ), Cs 1.3 Gd 0.3 Zr 1.7 (PO 4 ) 3 .
  • the thermal barrier coating includes surface treatments through application of a top layer 172 to enhance smoothness or enhance erosion resistance or reduce surface porosity.
  • the thermal barrier coating includes a material to absorb thermal radiation at or near a surface of the insulating thermal spray coating 170.
  • the material to absorb thermal radiation is one of Phosphor bonded Al 2 O 3 , Phosphor bonded Cr or Fe doped Al 2 O 3 , Phosphor bonded SiO 2 , Phosphor bonded Cr or Fe doped SiO 2 , Phosphor bonded ZrO 2 , Phosphor bonded Cr or Fe doped ZrO 2 , or calcium magnesium aluminosilicate glass.
  • the material further comprises silicon carbide or silicon nitride.
  • the component is one of a piston crown, a combustion chamber, a valve face, an exhaust port, or an exhaust manifold section.
  • a method 300 for forming a thermal barrier coating includes applying 302 an insulating thermal spray coating where a chosen material of the insulating thermal spray coating has a thermal conductivity lower than 2 W/mK in fully dense form and the chosen material includes a coefficient of thermal expansion within 5 ppm/K of a coefficient of thermal expansion of a material of a component of the internal combustion engine upon which the coating is placed.
  • a surface treatment applies a top layer to the insulating thermal spray coating.
  • the insulating thermal spray coating is polished. The method then ends. Some embodiments may include only one or two of the depicted steps.
  • instances in this specification where one element is “coupled” to another element can include direct and indirect coupling.
  • Direct coupling can be defined as one element coupled to and in some contact with another element.
  • Indirect coupling can be defined as coupling between two elements not in direct contact with each other, but having one or more additional elements between the coupled elements.
  • securing one element to another element can include direct securing and indirect securing.
  • adjacent does not necessarily denote contact. For example, one element can be adjacent another element without being in contact with that element.
  • the phrase “at least one of’, when used with a list of items, means different combinations of one or more of the listed items may be used and only one of the items in the list may be needed.
  • the item may be a particular object, thing, or category.
  • “at least one of’ means any combination of items or number of items may be used from the list, but not all of the items in the list may be required.
  • “at least one of item A, item B, and item C” may mean item A; item A and item B; item B; item A, item B, and item C; or item B and item C.
  • “at least one of item A, item B, and item C” may mean, for example, without limitation, two of item A, one of item B, and ten of item C; four of item B and seven of item C; or some other suitable combination.
  • a system, apparatus, structure, article, element, component, or hardware “configured to” perform a specified function is indeed capable of performing the specified function without any alteration, rather than merely having potential to perform the specified function after further modification.
  • the system, apparatus, structure, article, element, component, or hardware “configured to” perform a specified function is specifically selected, created, implemented, utilized, programmed, and/or designed for the purpose of performing the specified function.
  • “configured to” denotes existing characteristics of a system, apparatus, structure, article, element, component, or hardware which enable the system, apparatus, structure, article, element, component, or hardware to perform the specified function without further modification.
  • a system, apparatus, structure, article, element, component, or hardware described as being “configured to” perform a particular function may additionally or alternatively be described as being “adapted to” and/or as being “operative to” perform that function.
  • the operations of the method(s) herein are shown and described in a particular order, the order of the operations of each method may be altered so that certain operations may be performed in an inverse order or so that certain operations may be performed, at least in part, concurrently with other operations.
  • instructions or sub-operations of distinct operations may be implemented in an intermittent and/or alternating manner.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Acoustics & Sound (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

Un revêtement de barrière thermique pour un moteur à combustion interne comprend un revêtement de pulvérisation thermique isolant, un matériau choisi du revêtement par pulvérisation thermique isolant ayant une conductivité thermique inférieure à 2 W/mK sous une forme totalement dense et le matériau choisi comprenant un coefficient de dilatation thermique dans 5 ppm/K d'un coefficient de dilatation thermique d'un matériau d'un composant du moteur à combustion interne sur lequel le revêtement est placé.
PCT/US2020/049771 2019-09-06 2020-09-08 Revêtements barrières thermiques pour moteurs à combustion interne WO2021046548A1 (fr)

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EP20861415.6A EP4017923A4 (fr) 2019-09-06 2020-09-08 Revêtements barrières thermiques pour moteurs à combustion interne

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US201962897184P 2019-09-06 2019-09-06
US62/897,184 2019-09-06

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Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
CN115261764B (zh) * 2022-08-24 2023-08-25 昆山西诺巴精密模具有限公司 一种航空发动机机匣涂层及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100136349A1 (en) * 2008-11-25 2010-06-03 Rolls-Royce Corporation Multilayer thermal barrier coatings
US8558194B2 (en) * 2009-04-10 2013-10-15 The Penn State Research Foundation Interactive coatings, surfaces and materials
WO2015183439A2 (fr) * 2014-05-27 2015-12-03 General Electric Company Revêtements abradables de molybdate de lanthane, leurs procédés de formation et d'utilisation
US20170089259A1 (en) * 2015-09-30 2017-03-30 Corning Incorporated Composite thermal barrier for internal combustion engine component surfaces
WO2017059155A1 (fr) * 2015-09-30 2017-04-06 Corning Incorporated Barrière thermique composite pour surfaces de chambre de combustion
WO2017087734A1 (fr) * 2015-11-20 2017-05-26 Federal-Mogul Corporation Composants de moteur isolés thermiquement et procédé de fabrication mettant en œuvre un revêtement céramique
US20170321559A1 (en) * 2016-05-09 2017-11-09 General Electric Company Thermal barrier system with bond coat barrier
WO2019084370A1 (fr) * 2017-10-27 2019-05-02 Tenneco Inc. Piѐces de moteur à combustion dotées d'un revêtement thermo-isolant dynamique et procédé de fabrication et d'utilisation d'un tel revêtement

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6177200B1 (en) * 1996-12-12 2001-01-23 United Technologies Corporation Thermal barrier coating systems and materials
JP2001521993A (ja) * 1997-11-03 2001-11-13 シーメンス アクチエンゲゼルシヤフト 製品、特にセラミックス断熱層を有するガスタービンの構造部材
EP1029101B1 (fr) * 1997-11-03 2001-09-12 Siemens Aktiengesellschaft Produit, en particulier composant d'une turbine a gaz, a couche thermo-isolante en ceramique, et procede pour obtenir ladit produit
US5876860A (en) * 1997-12-09 1999-03-02 N.V. Interturbine Thermal barrier coating ceramic structure
US8448194B2 (en) 2009-09-30 2013-05-21 Sap Ag Value container propagation in development tools, business process management, and business rules management solutions
US10578050B2 (en) * 2015-11-20 2020-03-03 Tenneco Inc. Thermally insulated steel piston crown and method of making using a ceramic coating
CA3030843C (fr) * 2016-06-15 2023-03-07 The Penn State Research Foundation Revetements formant barriere thermique
US20190194812A1 (en) * 2017-12-21 2019-06-27 GM Global Technology Operations LLC Gap-filling sealing layer of thermal barrier coating
US10851711B2 (en) * 2017-12-22 2020-12-01 GM Global Technology Operations LLC Thermal barrier coating with temperature-following layer

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100136349A1 (en) * 2008-11-25 2010-06-03 Rolls-Royce Corporation Multilayer thermal barrier coatings
US8558194B2 (en) * 2009-04-10 2013-10-15 The Penn State Research Foundation Interactive coatings, surfaces and materials
WO2015183439A2 (fr) * 2014-05-27 2015-12-03 General Electric Company Revêtements abradables de molybdate de lanthane, leurs procédés de formation et d'utilisation
US20170089259A1 (en) * 2015-09-30 2017-03-30 Corning Incorporated Composite thermal barrier for internal combustion engine component surfaces
WO2017059155A1 (fr) * 2015-09-30 2017-04-06 Corning Incorporated Barrière thermique composite pour surfaces de chambre de combustion
WO2017087734A1 (fr) * 2015-11-20 2017-05-26 Federal-Mogul Corporation Composants de moteur isolés thermiquement et procédé de fabrication mettant en œuvre un revêtement céramique
US20170321559A1 (en) * 2016-05-09 2017-11-09 General Electric Company Thermal barrier system with bond coat barrier
WO2019084370A1 (fr) * 2017-10-27 2019-05-02 Tenneco Inc. Piѐces de moteur à combustion dotées d'un revêtement thermo-isolant dynamique et procédé de fabrication et d'utilisation d'un tel revêtement

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
FAN ET AL.: "Deposition of Lanthanum Strontium Cobalt Ferrite (LSCF) Using Suspension Plasma Spraying for Oxygen Transport Membrane Applications", JOURNAL OF THERMAL SPRAY TECHNOLOGY, vol. 24, no. 6, August 2015 (2015-08-01), pages 1081 - 1092, XP035525154, DOI: 10.1007/s11666-015-0269-4 *
NEGAHDARI ET AL.: "Tailoring the microstructure of reaction-sintered alumina/lanthanum hexaaluminate particulate composites", JOURNAL OF THE EUROPEAN CERAMICS SOCIETY, vol. 30, 2010, pages 1381 - 1389, XP026892966, DOI: 10.1016/j.jeurceramsoc.2009.10.010 *
PETKOV V.I, ORLOVA A.I: "Crystal-Chemical Approach to Predicting the Thermal Expansion of Compounds in the NZP Family", INORGANIC MATERIALS, vol. 39, no. 10, 2003, pages 1013 - 1023, XP055802262 *
See also references of EP4017923A4 *

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Publication number Publication date
EP4017923A1 (fr) 2022-06-29
EP4017923A4 (fr) 2023-06-14
US20220034257A1 (en) 2022-02-03
US20210071571A1 (en) 2021-03-11
US11434816B2 (en) 2022-09-06
US11519329B2 (en) 2022-12-06

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